EP0527035B1 - Procédé de préparation de fullerène - Google Patents

Procédé de préparation de fullerène Download PDF

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Publication number
EP0527035B1
EP0527035B1 EP92307121A EP92307121A EP0527035B1 EP 0527035 B1 EP0527035 B1 EP 0527035B1 EP 92307121 A EP92307121 A EP 92307121A EP 92307121 A EP92307121 A EP 92307121A EP 0527035 B1 EP0527035 B1 EP 0527035B1
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process according
substance
carbon
gas
plasma
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German (de)
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EP0527035A1 (fr
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Toyonobu Yoshida
Keisuke Eguchi
Kenichi Yoshie
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Mitsubishi Chemical Corp
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Mitsubishi Chemical Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/152—Fullerenes
    • C01B32/154—Preparation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/152—Fullerenes
    • C01B32/156—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B23/00—Single-crystal growth by condensing evaporated or sublimed materials
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B23/00—Single-crystal growth by condensing evaporated or sublimed materials
    • C30B23/02—Epitaxial-layer growth
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/02—Elements

Definitions

  • the present invention relates to a process for preparing fullerenes such as a C60 or C70 fullerene. These compounds can be used as high lubricants, high-hardness materials and catalyst carriers.
  • the C70 substance is produced along with the C60 substance in the soot.
  • the C60 and C70 substances can be chromatographically separated with a solvent such as hexane by using a column of, for example, C18 silica gel or alumina for reversed phase-chromatography.
  • the present invention provides a process for preparing fullerenes which comprises introducing a carbonaceous material, in the form discrete particles in the suspended state containing less than 0.05 wt% of particles exceeding 100 »m in particle size, along with a gas into hot plasma to heat and evaporate the carbon.
  • Fullerenes such as C60 and C70 fullerenes can be produced continuously according to the present invention with uniform composition and in a high yield.
  • the carbonaceous material is any material which is mainly composed of carbon. In certain cases such a material may contain elements other than carbon, such as hydrogen or oxygen, but a material with a high carbon content is preferably used. Typical examples of such material are carbon black, graphite powder, carbon fiber, coal powder, active carbon powder, charcoal powder and coke powder. A carbonaceous material of a low H/C or O/C molar ratio is preferred. When using a material in which the H/C or O/C molar ratio is less than 10 ⁇ 2, it is possible to obtain the fullerenes in an even higher yield. Graphitized carbon black, graphite powder and graphitized carbon fiber can be exemplified as such a material.
  • the form of the carbonaceous material is not specifically limited so long as it can be easily evaporated after being heated in hot plasma. In the present invention, however, it is essential that the material be introduced into hot plasma in a suspended state and having a particle size of not more than 100 »m (i.e the content of the particles with a particle size of more than 100 »m is less than 0.05 wt%, preferably 0.01 to 20 »m, as measured according to the measuring method of dust particle-size distribution in an exhaust gas of JIS K 0302-1989.
  • the carbonaceous material contains not less than 60 wt.% of particles having a particle size of less than 20 »m, preferably 0.01 to 10 »m.
  • the particles stay in an aggregated state, so to suspend the fine particles mentioned above it is recommended to use a jet crusher or a disperser having high-speed rotor blades, if necessary in combination with a classifier such as a cyclone.
  • a carbonaceous material constituted entirely by 13C By using a carbonaceous material constituted entirely by 13C, a C60 substance and/or a C70 substance composed of 13C alone can be produced.
  • Any available source can be used for generating hot plasma in the present invention, so long as the source is capable of generating hot plasma of a sufficiently high temperature due to the evaporation of carbon and also having sufficient heat conductivity and retention time.
  • Typical examples of such a source are a DC jet, a high-frequency inductive coupled-plasma (ICP), a hybrid-type combining a DC jet and ICP, and a hybrid-type combining 2 or 3 sets of ICP arranged in series.
  • Such hot plasma is capable of easily evaporating carbon having a sublimation point of around 3,550°C.
  • the hot plasma used in the present invention thus has high heat conductivity and long retention time. It is also advantageous in that the hot plasma in the present invention is capable of elevating the evaporating efficiency of the carbon source and enhancing the precipitating efficiency of the C60 substance and/or the C70 substance.
  • the system pressure is generally selected from 10 Torr (1.3 kPa) to 2 atm (202 Kpa).
  • the high-frequency inductive coupled-type plasma (ICP) or a hybrid-type composed of ICP and a DC jet on a small-scale ICP is preferred because of the longer retention time.
  • the lower limit of the rate of which the carbonaceous material may be introduced is the amount which enables precipitation and recovery of a required amount of carbon.
  • the upper limit is the rate which makes it possible to provide a sufficient calorific value due to the evaporation of carbon without extinguishing the plasma.
  • the rate at which the carbonaceous material introduced in the present invention is 0.01 g/min or more.
  • the upper limit depends on the input power for forming the hot plasma flow-zone and the plasma generating system, but in the case of ICP, for instance, the rate is not more than 10 g/min when the input power is 20 kw and not more than 100 g/min when the input power is 50 kw.
  • Figs. 1 and 2 The plasma reaction systems used in the present invention are shown in Figs. 1 and 2.
  • the carbon heated and evaporated in hot plasma is reprecipitated as the gas is cooled spontaneously at the tail flame portion of the plasma.
  • a cooling gas may be used for forcing a quick cooling.
  • An inert gas such as Ar or He can be used as the plasma gas.
  • a carbonaceous material preferably one having a high carbon content such as carbon black or graphite, is introduced while entraining the carbonaceous material in a stream of inert gas from the top of the reaction system.
  • the flow rate of the inert gas is not critical in the present invention, but is preferably from 5 to 500 Nl/min.
  • the product is deposited on a "pyrex" (trade mark) tube disposed downstream of the hot plasma, so the product is scraped away from the "pyrex” tube and recovered.
  • the product is, also, recovered from a filter set further downstream than the "pyrex" tube.
  • the cooling rate can be controlled by the rate of feeding gas from a cooling gas inlet (6) shown in Fig. 1.
  • a cooling gas may introduced into the system to conduct quick cooling for precipitating the carbon heated and evaporated in hot plasma.
  • the rate feeding the cooling gas may be the same as that commonly used for cooling in ordinary hot plasma. It is preferable to set the feeding rate of the cooling gas at 10% or higher, more preferably 50% or higher, than the flow rate of the plasma gas.
  • An inert gas such as Ar, He, Ne or Xe or a gas which hardly reacts with carbon, such as N2, is preferably used as the cooling gas.
  • gas hydrogen oxygen, carbon monoxide, a halogen such as chlorine, carbon dioxide, a nitrogen oxide such as nitrogen dioxide, a sulfur compound such as sulfur dioxide, or various other gases in an amount which does not cause perfect gasification of carbon.
  • a halogen such as chlorine, carbon dioxide, a nitrogen oxide such as nitrogen dioxide, a sulfur compound such as sulfur dioxide, or various other gases in an amount which does not cause perfect gasification of carbon.
  • a water-cooled base plate may also be disposed immediately beneath the plasma zone to increase the cooling speed.
  • preparation of the C60 substance and/or the C70 to substance has been set as the primary objective, and it has been confirmed that these compounds can be produced in hot plasma. It is conceivable that a series of allotropes, that is, other fullerene such as a C24 substance, C28 substance, C32 substance, C50 substance, C84 substance, C120 substance, C240 substance and C540 substance, would also be produced by the same method.
  • both the C60 substance and the C70 substance are produced concurrently with each other, their separation can be effected by any suitable conventional method, but usually they are chromatographically separated with a solvent such as hexane using a column of, for example C16 silica gel or alumina in reversed phase chromatography.
  • a solvent such as hexane
  • fullerenes containing a metal or an element other than carbon, such as boron, nitrogen or phosphorus may be produced by incorporating the metal or element in the starting material in the preparation process.
  • the amount of the metals which are contained in the fullerenes or which replace the part of the fullerenes is preferably 0.1 to 50 wt.%.
  • a metal which has a small ionic radius for example an alkali metal such as lithium, potassium, sodium, rubidium or cesium; an alkaline earth metal such as beryllium, magnesium, calcium, barium or strontium; a metal of Group IIIa of the Periodic Table such as scandium, yttrium or lanthanum; a lanthanoid metal such as neodymium, samarium, europium, terbium or ytterbium; or a transition metal of the 4th Period of the Periodic Table such as titanium, vanadium, chromium, manganese, iron, cobalt, nickel or zinc.
  • an oxide, halide, carbonate, bicarbonate, oxalate, sulfide, sulfate or nitrates of the above-mentioned metals may, for example, be used.
  • fullerenes in which the carbon atoms thereof are replaced with nitrogen by introducing the carbon particles into the plasma gas mixed with nitrogen.
  • Fullerenes in which the carbon atoms thereof are replaced with nitrogen can be also produced by introducing a nitrogen-containing compound such as pyridine or quinoline in the form of a mist into the plasma gas.
  • the C60 substance and/or C70 substance can be obtained in a high yield (such as 1 % or higher). They can also be mass-produced continuously and efficiently.
  • the C60 substance can be effectively utilized as, for example, a lubricant, high-hardness material or cell material.
  • 1 denotes a DC arc unit
  • 2 denotes a high-frequency arc unit
  • 3, 4, 5, 6 and 7 denote gas inlets
  • 8 denotes a cooling water conduit
  • 9 denotes a cooling water discharge pipe
  • 10 denotes a pyrex tube.
  • a power of 5 kw was applied to the DC arc unit (1) and 20 kw (4 MHz) to the high-frequency arc unit (2) as input power.
  • the reactor was previously evacuated to 0.05 Torr (6.7 Pa) by a hydraulic vacuum pump. After confirming that air leak into the system was not more than 0.05 cc/min, plasma gas was introduced into the reactor. Ar was used as the plasma gas. The gas was introduced from a gas inlet at a feeding rate of 10 Nl/min for the DC arc and at a feeding rate of 30 Nl/min as a whirling flow for the high-frequency arc.
  • Ar gas was also introduced from a gas inlet (6) at a feeding rate of 50 Nl/min.
  • Graphitized carbon black #4000B (produced by Mitsubishi Kasei Corporation) was used as the starting carbonaceous material. It was supplied into a gravity classifier while entraining the graphitized carbon black in a 2 Nl/min Ar gas stream from an airtight feeder and, after getting rid of particles having a particle size of more than 100 »m, the resultant carbon black was introduced into the system from a fine powder inlet (5) above the plasma.
  • the particle feeding rate was 2 g/min, and the pressure in the system was 760 Torr (101 kPa).
  • the carbon black was perfectly decomposed in the plasma and then cooled downstream by the Ar gas stream at 50 Nl/min, which caused reprecipitation of the carbon.
  • the products which were deposited on a downstream pyrex tube and collected by a filter were recovered.
  • the recovered product was extracted with benzene to obtain a reddish-purple extract solution. When this solution was subjected to mass spectrometry, peaks at 720 amu and 840 amu were detected.
  • a power of 5 kw was applied to the DC arc unit (1) and 17 kw (4 MHz) to the high-frequency arc unit (2) as input power.
  • the reactor was previously evacuated to 0.05 Torr (6.7 Pa) by a hydraulic vacuum pump. After confirming that air leak into the system was not more than 0.03 cc/min, plasma gas was introduced into the reactor.
  • argon gas was introduced at a feeding rate of 4 Nl/min from a gas inlet (3).
  • argon gas was also introduced as a whirling flow at a feeding rate of 26 Nl/min from a gas inlet (4).
  • a mixture of 12 Nl/min argon gas and 14 Nl/min helium gas was introduced in the radial direction from a gas inlet (6).
  • a filter was set downstream, and was connected to a vacuum pump via a flow control valve.
  • the pressure in the system was kept at 600 Torr (80 kPa) by adjusting the opening of the valve.
  • Graphitized carbon black was used as the starting material as in Example 1. It was entrained in a 10 Nl/min stream of Ar gas, which was ejected from a 2 mm ⁇ fine tube and hit against a downstream metal plate to cause dispersion. After getting rid of particles having a particle size of more than 100 »m by a gravity classifier, the resultant carbon black was introduced into the system at a feeding rate of 0.5 g/min from an inlet (5).
  • Determination of the particle size of the suspended particles in the gas according to JIS K-0302-1989 disclosed that particles with sizes of less than 10 »m accounted for 75 wt.% based on the whole particles.
  • the products which deposited on the wall of a downstream chamber and collected by a filter set further downstream were recovered.
  • the recovered product was assayed in the same way as in Example 1.
  • the C60 substance and C70 substance could be recovered at 5% and 2% by weight, respectively, based on the introduced carbon black.
  • Example 2 An experiment similar to Example 2 was carried out with the same gas flow rate, the same plasma power and the same material introducing method as in Example 2 except for adjusting the pressure in the system to 260 Torr (35 kPa).
  • Example 2 An experiment similar to Example 2 was carried out except that non-graphitized carbon black #40 (produced by Mitsubishi Kasei Corporation) was used as the starting material.
  • the particle size of the suspended particles immediately before introduction of the material was the same as in Example 2.
  • the C60 substance and C70 substance could be recovered at 2% and 0.5% by weight, respectively, based on the introduced carbon black.
  • Example 2 An experiment similar to Example 2 was carried out using as starting material the ground and classified powder of calcined needle coke (produced by Mitsubishi Kasei Corporation).
  • the starting particulate material in a suspended state immediately before introduction into the hot plasma reactor was such that 96 wt.% of the particles had a particle size of not more than 10 »m. There were no particles having a particle size of more than 100 »m.
  • the C60 substance and C70 substance could be recovered at 2% and 0.5% by weight, respectively, based on the starting powder.
  • Example 2 An experiment similar to Example 2 was carried out using as starting material carbon black #4000B (produced by Mitsubishi Kasei Corporation) which had been mixed with 20 wt.% of yttrium oxide. As a result, about 2 wt.% of toluene extract was obtained from the recovered solid product. It was confirmed by ESR that this extract contained yttrium. Mass spectrometry of the extract detected YC82, Y2C82 and Y2C84 peaks.
  • Example 2 The same experiment as Example 2 was carried out except that carbon black #4000B (produced by Mitsubishi Kasei Corporation) which had been mixed with 2 wt.% of hexagonal boron nitride was used as starting material. As a result, about 5 wt.% of toluene extract was obtained from the recovered solid. Elemental analysis of the extract confirmed that this extract contained boron. Mass spectrometry of the extract detected C59B, C58B2, C57B3 and C56B4 peaks.
  • carbon black #4000B produced by Mitsubishi Kasei Corporation
  • Example 2 The same experiment as Example 2 was carried out except that carbon black #4000B (produced by Mitsubishi Kasei Corporation) was used as starting material, that a mixture of 0.1 Nl/min of nitrogen and 25 Nl/min of argon for the plasma was introduced into the system from gas inlet (4), and that 23 Nl/min of argon was introduced in the radial direction from gas inlet (6). As a result, about 5 wt.% of toluene extract was obtained from the recovered solid. It was confirmed by elemental analysis that the extract contained nitrogen, and mass spectrometry of the extract detected C59N, C58N2, C57N3 and C56N4 peaks.
  • carbon black #4000B produced by Mitsubishi Kasei Corporation
  • Example 2 The experiment of Example 2 was carried out except for using as starting material carbon black #4000B (produced by Mitsubishi Kasei Corporation) which had been mixed with 5 wt.% of potassium iodide. As a result, about 5 wt.% of toluene extract was obtained from the recovered solid product. It was confirmed by ESR that the extract contained potassium. Mass spectrometry of the extract detected KC60, KC70 and KC82 peaks.
  • Example 2 The same experiment as Example 2 was carried out except that carbon black #4000B (produced by Mitsubishi Kasei Corporation) which had been mixed with 5 wt.% of calcium carbonate was used as starting material. As a result, about 5 wt.% of toluene extract was obtained from the recovered solid product. It was confirmed by ESR that the extract contained calcium. Mass spectrometry of the extract detected CaC60, CaC70 and CaC82 peaks.
  • Example 2 The experiment of Example 2 was carried out except for using as starting material carbon black #4000B (produced by Mitsubishi Kasei Corporation) which had been mixed with 5 wt.% of iron powder. As a result, about 5 wt.% of toluene extract was obtained from the recovered solid product. It was confirmed by ESR that the extract contained iron. Mass spectrometry of the extract detected FeC60, FeC70 and FeC82 peaks.
  • Example 2 An experiment similar to Example 2 was carried out except for using as starting material pulverized carbon black which had not been subjected to classification and which contained 40 wt.% of particles having a particle size of 100-1,000 »m. As a result, the C60 substance and C70 substance could be recovered at only 0.3% and 0.1% by weight, respectively, based on the introduced carbon black.

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  • Organic Chemistry (AREA)
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  • Inorganic Chemistry (AREA)
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Claims (10)

  1. Procédé de préparation de fullerènes, selon lequel on introduit une matière carbonée sous forme de particules discrètes à l'état de suspension, contenant moins de 0,05 % en poids de particules ayant une taille particulaire supérieure à 100 »m, en association avec un gaz, dans un plasma chaud, afin de chauffer et d'évaporer le carbone.
  2. Procédé selon la revendication 1, dans lequel le carbone chauffé et évaporé dans le plasma chaud, est refroidi à l'aide d'un gaz réfrigérant.
  3. Procédé selon la revendication 1 ou 2, dans lequel la matière carbonée ne contient pas moins de 60 % en poids de particules ayant une taille particulaire inférieure à 20 »m.
  4. Procédé selon l'une quelconque des revendications précédentes, dans lequel la source génératrice de plasma chaud, est un jet généré par courant continu (DC), un plasma de couplage inductif à haute fréquence (ICP), un type hybride combinant un jet DC en plasma ICP ou un couple hybride combinant deux ou trois dispositifs à plasma ICP en série.
  5. Procédé selon l'une quelconque des revendications précédentes, dans lequel la matière carbonée est introduite selon un débit inférieur à 0,01 g/mn.
  6. Procédé selon l'une quelconque des revendications précédentes, dans lequel le gaz introduit avec la matière carbonée est Ar ou He.
  7. Procédé selon l'une quelconque des revendications précédentes, selon lequel la matière carbonée est du noir de carbone, de la poudre de graphite, des fibres de carbone, de la poudre de charbon, de la poudre de carbone actif, de la poudre de charbon de bois ou de la poudre de coke.
  8. Procédé selon l'une des revendications précédentes, dans lequel le fullerène est un fullerène en C₆₀ ou C₇₀.
  9. Procédé selon l'une quelconque des revendications 1 à 7, dans lequel on introduit également dans le plasma chaud, un métal ou un composé de métal, du bore ou un composé du bore, de l'azote ou un composé de l'azote, ou du phosphore ou un composé du phosphore.
  10. Procédé selon l'une quelconque des revendications précédentes, comprenant en outre la séparation du fullerène désiré.
EP92307121A 1991-08-07 1992-08-04 Procédé de préparation de fullerène Expired - Lifetime EP0527035B1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP198055/91 1991-08-07
JP19805591 1991-08-07
JP111826/92 1992-04-30
JP4111826A JPH05124807A (ja) 1991-08-07 1992-04-30 フラーレン類の製造方法

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EP0527035A1 EP0527035A1 (fr) 1993-02-10
EP0527035B1 true EP0527035B1 (fr) 1995-05-10

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DE (1) DE69202419T2 (fr)

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1993023331A1 (fr) * 1992-05-15 1993-11-25 Lane David R Iii Procede de production de fullerenes utilisant du plasma
US5876684A (en) * 1992-08-14 1999-03-02 Materials And Electrochemical Research (Mer) Corporation Methods and apparati for producing fullerenes
DE4302144C2 (de) * 1993-01-27 1996-01-25 Lipprandt Michael Dipl Ing Verfahren zur Erzeugung von Kohlenstoff-Fullerenen aus kohlenstoffhaltigen festen Rohstoffen und Vorrichtung dazu
JPH0797204A (ja) * 1993-09-28 1995-04-11 Sansha Electric Mfg Co Ltd フラーレンススの回収装置
DE4333683A1 (de) * 1993-10-02 1995-04-06 Till Keesmann Verfahren und Vorrichtung zur Herstellung von Fullerenen
FR2764280B1 (fr) * 1997-06-06 1999-07-16 Yvan Alfred Schwob Procede pour la fabrication de carbone 60
DE102009018350A1 (de) * 2009-04-23 2010-10-28 Aimes Gmbh Umwandlungsvorrichtung zum Umwandeln von Biomasse in Kohlenwasserstoffverbindungen, Verfahren zum wenigstens teilweisen Umwandeln von Biomasse in Kohlenwasserstoffverbindungen, Nutzgas und Feststoff, sowie Verfahren zum wenigstens teilweisen Umwandeln von kontaminierten Stoffen in CO2
JP5716155B2 (ja) * 2010-08-30 2015-05-13 国立大学法人名古屋大学 ナノカーボン製造用粉末及び金属内包フラーレンの生成方法
WO2019082755A1 (fr) 2017-10-27 2019-05-02 昭和電工株式会社 Fibres de carbone, et procédé de fabrication de celles-ci
EP3702518A4 (fr) 2017-10-27 2020-12-23 Showa Denko K.K. Fibres de carbone, et procédé de fabrication de celles-ci
JPWO2019082757A1 (ja) * 2017-10-27 2020-11-12 昭和電工株式会社 炭素繊維及びその製造方法

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US7494638B1 (en) * 1990-08-30 2009-02-24 Mitsubishi Corporation Form of carbon

Non-Patent Citations (1)

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Title
MACKAY A. L.: "CARBON CRYSTALS WRAPPED UP.", NATURE, NATURE PUBLISHING GROUP, UNITED KINGDOM, vol. 347., no. 6291., 27 September 1990 (1990-09-27), United Kingdom, pages 336 - 337., XP000147104, ISSN: 0028-0836, DOI: 10.1038/347336a0 *

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DE69202419D1 (de) 1995-06-14
DE69202419T2 (de) 1995-10-05
EP0527035A1 (fr) 1993-02-10
JPH05124807A (ja) 1993-05-21

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